Compounds [Cu2(trans-oxen)(tp)]n·2nH2O (1·2nH2O), [{Cu2(trans-oxpn)(H2O)2}{Cu2(trans-oxpn)}(isophth)2]n·7nH2O (2·7nH2O) and [Cu2(trans-oxen)(phth)]n·2nH2O (3·2nH2O) [H2oxen = N,N′-bis(2-aminoethyl)oxamide, H2oxpn = N,N′-bis(3-aminopropyl)oxamide, tp = terephthalate, isophth = isophthalate and phth = phthalate] were obtained from the self-organization of trans-oxamidato-bridged dicopper(II) building blocks [Cu2(trans-L)]2+ (L = oxen or oxpn) and phenyldicarboxylate spacers with differently oriented carboxyl groups and their crystal structures determined. All the compounds consist of solvated water molecules and 2-D polymeric coordination networks containing rectangular, H-shaped mosaics and distorted rectangular grids for 1, 2, and 3, respectively. In addition, variegated hydrogen bonds involving solvated water molecules link the 2-D nets into 3-D frameworks. New bridging modes were discovered for the three isomeric phenyldicarboxylates. Magnetic calculations on 2·7nH2O showed that the planar oxamidato bridge transmits antiferromagnetic interactions between the Cu(II) ions.
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